Acylated aminoalcohol esters of carbonic acid



' Patented Sept. 11, 1945 ACYLATED AMINOALCOHOL ESTERS F CARBONIC ACIDMelvin De Groote, University City, and Bernhard Keiser, Webster Groves,Mo., assignors to Petrolite Corporation, Ltd., corporation of DelawareWilmington, Del.,.a

No Drawing. Original application March 9, 1943. Serial No. 478,594.Divided and this application 7 Claims.

This invention relates to a new composition of matter, our presentapplication being a division of our pending application Serial No.478,594,-

filed March 9, 1943, which subsequently matured Tag. S. Patent No.2,373,174, dated April 10,

The main object of our invention is to provide a new material orcomposition of matter, that is particularly adapted for use as a'demnlsifier in the resolution of crude oil emulsions, butwhich 1Scapable of use for various other purposes. For instance, the saidmaterial may be used as a break inducer in doctor treatment of the kindintended to sweeten gasoline. Certain of the compositions of matterherein described are of value as surface tension depressants in theacidification of calcareous oil-bearing strata by means of strongmineral acid, such as hydrochloric acid. Similarly, some members areeffective as surface tension depressants, or wetting agents in theflooding of exhausted oil-bearing strata.

Another object of our invention is to provide a novel method forproducing said new material or composition of matter.

The new material or composition of matter herein described, consists ofacylated derivatives obtained by reaction between a low molal dialkylcarbonate, particularly diethyl carbonate, and

- alkanolamines, including the ether type, i. e., such alkanolamines inwhich a carbon atom chain is interrupted at least once .by an oxygenatom. Such alkanolamines may have an alicyclic radcal, such as acyclohexyl radical, an aralkyl radical, or an aryl radical attached toan amino mtrogen atom. In other words, one is not limited to the use ofmaterials such as monoethanol- September 2, 1943, Serial No. 501,028

amine,- diethanolamine, triethanolamine, monopropanolamine,dipropanolamine, tripropanolamine, monobutanolamme, dibutanolamine,tributanolamme, or ether type derivatives obtained by treating thepreceding with ethylene oxide,

propylene'oxide, glycid, or the like.

If desired, one may as amylamine, octaylamine, decylamine, or the like,with one or more moles of ethylene oxide,.

propylene oxide, or the like, so as to obtain a su table reactant. Thesame is true in regard to alicyclic amines. such as cyclohexylamine, orin regard t aralkylamines. to various arylamines, such as aniline, andthe like, It is to be noted that the alkanolamine need not be a tertiaryamine, but maybe a primary or a secondary amine Thus, the expressionalkanolamine is employed in the present instance to indicate-mat theremust be present treat an alkylamine, such It is also true in regard 'atleast one nitrogen-linked alkanol group, in-

cluding the type, as previously stated, in which the carbon atom chainis interruptedat least once by an oxygen atom. One-may, of course. usepolyamino compounds, such as, for example, the products obtained bytreating ethylene diamine with ethylene oxide so as to introduce atleast 4 hydroxyethyl radicals. The acyl radical may be introduced at anyconvenient stage, for instance, before the amino-containing reactant hasbeen combined with the low molal dialkyl carbonate, or afterwards. Otherlow molal carbonates which may be employed include dimethyl ester,methyl ethyl ester; methyl propyl ester, dipropyl ester, dibutyl ester,etc.

Theacyl group which is introduced is derived from detergent-formingmonocarboxy acids containing'8 carbon atoms or more, and not more than32 carbon atoms, and are characterized by the fact that they combinewith. alkalis to produce soap orsoap-like materials. Thesedetergent-forming acids include fatty acids, resin acids, petroleumacids, etc. For the sake of convenience, these acids will be indicatedby the formula R.CO0H. Certain derivatives of detergent-forming acidsreact with alkali to produce soap or soap-like materials, and are theobvious equivalent of the unchanged or unmodified deterjected to variousmodifications, provided'such modifications still retaindetergent-forming action may take place. For example, there may be aformation of an urethane and an amino ester simultaneously.

In view of what is said hereinafter, it is apparent that the compoundscontemplated herein may be considered as acylation derivatives of estersof carbamic and carbonic acids, and more particularly; esters containingat least one nitrogen-linked aikanol radical, and in which the acylradical is that of. carboxy'acid having at least 8 and not more than 32carbon atoms.

For the sake of clarity, the following reaction types are presented asillustrating the class of compounds formed. In all instances, they repadetergent-forming mono- 2 asscaoa resent intermediate. products and areacylated more complicated types of materials or chemisubsequently: calcompounds which may be used as demulsi- Hcim 0 v 011cm. i o Canon ricimo-f c nlo i o(hm /NCIH0H mmogtifomn'. n iommN oncim oncan canon 03013 i n9 01111011 clmo 'n C2H|0.. :0.C|Hg ngocimncimogn cimoitigocm n ioc,mN011mm cimon ondary amines, a more complicated series of reillustrateadded examples: actions may take place. Indeed, in the ordinary 5 coursethe result 01' reaction 18 a mixture of var- OHCiHf i ious products. Itis particularly true when the N511 c moidomm final acylated product isused as an intermediate m diethyl phthalate, that it is immaterial formany 20 I purposes, whether a single resultant is obtained Ioncimlr'olmofn pimo i omm v v H ent application either as newcompositions of 01340003 matter, new chemical compounds, or as demulsi-1;IOiHi0;'H+o,H.0Ec.,-'oc,11. +Hoc,rnN ilers for water-m-oil emulsions.011cm @011 The foregoing is illustrated by considering a very simpleaspect, for instance, a reaction in- I volving diethanolamine anddiethyl carbonate. 1 l EH+ 2H|-o- .0.C|H5 At least three possiblereactions suggest themselves immediately:

C1H4OH 0HC|H4 czHloH r t v o v NEH 0:11.05 ocim H5N C H "";':g 011cm.canon 12.00 011mm 0 -H t "g' II: "I ClHIOH /NI:H CI-HIO:C:'CIHB HOECIHINI o CIR-0H C H gg' gg'gig 1; "i 011cm o cimon 40 RCON/ i; -I:' ff:f5

Ncimion+cimiocoicmfinoicim OQC'R H 13.01! noc The same reaction as aboveillustrated will take INTERMEDIATE PRODUCT I place in connection withother materials, such as Exam 1 1 dipropanolamine, dibutanolamine, andalso in p 8 connection with secondary amines of the type W po nd molesof triethanolamine were ethyl ethanolamine, ethyl propanolamine, ethylheated for approximately 6-12 hours under a reu n l mi Dropylethanolamme, propyl proux condenser with one pound mole of diethylpanolamine, cyclohexyl ethanolamine, benzyl' carbonate The refluxingtemperature was'apbutanolamine, monopentanolamine; monohexunreacteddiethyl carbonate. In its simplest asanolamine, etc. I pect the reactionmay be illustrated thus:

Reconsidering the three, reactions immediately In reactions involvingalkanol primary or see.- tiers for water-in-oil emulsions. The followingpreceding, it is'obvious that they may be con-- 9 01mm! sidered assubstituted ureas, substituted ure- Nclmoiu+0,H.o5c5ocim+n5oo,mN{ Ithanes, and carbonic acid esters. The urethanes omhm/ CmoH are, ofcourse, esters of carbamic acid. It is also obvious that the products ofreaction above de- Imznmcnrarr: Pnopucr scribed, the esters, urethanes,the substituted Example 2 ureas, etc, can be treated with ethyleneoxide, or a some other reagent having a reactive ethylene T sameprocedure was followed in n e oxide ring, and subsequently, acylatedwithahigh media Product Example Precedingexcept onnection, p that onepound mole of triethanolamine was emerence is made to U. s. Patent No.2,083,221, Dgv r t ree pound moles of diethyl carbonucts thereincontemplated are acylated deriva- INTERMEDIATE PRODUCT tives ofsubstituted ureas, it is obvious that such Exam le ype of material isnot contemplated in the pres- Y ent instance, although we havediscovered that The product obtained in Intermediate product,

such material of a type contemplated in said Example 2, preceding, washeated further until aforementioned De Groote patent can be reacted theresultant mass represented a viscous material Imanucnm'rr: PaonucrExample 4 Triethanolamine, which had been treated with ethylene oxide inthe ratio of three moles of ethylene oxide for one mole oftriethanolamine, was substituted as the tertiary amine in the precedingexamples.

of diethanolamine were reacted with one pound mole of diethyl carbonatein the same manner as described in Intermediate product, Example 1,preceding. Analysis indicated that the final product contairiedapproximately 50% 01. an urethane or substituted urea and 50% of anamino ester.

INTERMEDIATE Pnonuc'r Example 7 Two pound moles of hydroxyethyl ethylenediamine were reacted with one pound mole 01' diethyl carbonate in themanner described under Intermediate product, Example 1, preceding.

INTERMEDIATE Pxonuc'r Example 8 The same procedure was followed as inthe preceding example, except that tetraethonal tetra- Iwo pound molesplace. For these reasons, subsequent acylatlon of intermediate productsof the kind previously described is best conducted by a nonacidic fattyacid derivative, rather than the fatty acid derivativeitselt. In otherwords, if one attempts to acylate materials of the kind previouslydescribed by means of oleic acid, ricinoleic acid, abietic acid,naphthenic acid, or the like, one finds that decomposition takesplace,under conditions required to give the desired resultant. One suitableprocedure is to resort to a functional equivalent of the acid, such asan ester or amide. This means that for practical purposes it is mostconvenient to use the higher fatty acids as a source of the high molalmonocarboxy detergent-forming radical, for the reason that such acidsare available in the form of an ester, i. e., the glyceride. In otherinstances, and especially when the reaction takes place at a decidedlylower temperature, one may employ a low molal mono- I hydric alcoholester of the detergent-forming acid, such as a methyl ester, an ethylester, or a ethylene pentamine was substiuted in place of hydroxyethylethylene diamine. I

INTERMEDIATE Pxonuc'r Example 2 I One pound mole of hydroxyethylethylene diamine was treated with three to five pound moles of ethyleneoxide, so as to convert all amino hydrogen atoms to hydroxyethylradicals. The product so obtained was substitutedfor hydroxyethylethylene diamine in Example 7, preceding.

In'raamsnrsra Paonoc'r Example 10 Tris(hydroxymethyl) stituted fortriethanolamine in Intermediate product, Example 1, preceding. When thisreactant was used, the yield was considerably less than with previousexamples, especially those in which triethanolamine was reported.Approximately /2% of sodium bicarbonate was added as a catalyst duringthe reaction.

In the manufacture of any compound involving diethyl carbonate, it isobvious that care must be taken that the carbonate or some other similarcarbonate such as dipropyl carbonate, is not decomposed by the presenceof an acidic reagent under conditions which would tend towardsliberating carbon dioxide. It is not always possible to predict thestability of the more complex carbonates or derivatives of the kindwhich have been described and illustrated by the examples 0!Intermediate products immediately preceding. Indeed, it is not alwayspossible to predict the stability of diethyl carbonate towards aqueousacids, even at normal room temperature. The best test in any instance isan actual laboratory experiment to determine whether or notdecomposition'and liberation of carbon dioxide takes aminomethane wassub- I hydroxy hydrocarbon radical or particularly desirable reactants.

propyl ester of the fatty acid or detergent-forming acid. In otherwords, ethyl ricinoleate, ethyl oleate, ethyl naphthenate, ethylabietate, etc., are The methyl esters and propyl esters are alsodesirable. The corresponding amides derived by reaction between one moleof the ,acidsand ammonia may also be used with the subsequent liberationof ammonia during thereaction. What has been said in this connection isreadily illustrated by subsequent examples.

Another procedure to obviate such difliculties of decomposition hasalready beensuggested by the formulas or reactions previously presented.One solution resides in introducing the acyl' radical of the high molaldetergent-forming acid into the desired amino molecule or compound priorto reaction with diethyl carbonate, or its equivalent. For instance, itis well known that any or the monocarboxy detergent-forming acids or thekind herein contemplated as such, or in any equivalent form, includingthe acyl chloride, amide or acid can be reacted with a variety ofprimary or secondary amines containing an alkanol radical, such asmonoethanolamine, diethanolamine, monopropanolamine, dipropanolamine,tris(hydroxymethyl) aminomethane, or the like, to produce amides inwhich there is present at least one amino radical. Other 5 tablereactants of this type include ethylethanolamine,cyclohexylethanolamine, phenylethanolamine, benzylethanolamine, and thelike. The manufacture of such amides'is well known and requires nofurther elaboration, although some subsequent examples may illustratethe formation of such amides. by the oxyalkylation of an 'amide.

In regard to the acylated aminoalcohols used as reactants, one type, amonoamino type, is described in U. S.- Patent No. 2,225,824, datedDecember 24, 1940, to De Groote and Wirtel. Said patent describes indetail the manufacture of compounds of the following formula:

(R.coo.c.Ht.).

N(T) II" (or anismin which R'.COO represents the oxyacyl radical derivedfrom a monobasic detergent-forming acid; T represents a hydrogen atom ora nonthe acylated radical obtained by replacing a hydrogen atom orthehydroxyl group of an alkylol radical by the acyl radical of amonobasic carbon acid having less than 8 carbon atoms: 1: represents asmall whole number which is less than 10; m represents the numeral 1, 2or 3; m represents the numeral so as to convert it into an aminoalcohol0, 1 or 2; and m" represents the numeral 0, 1 or 5 far that there aretwo or more amino nitrogen 2, with the proviso that m-j-m l-m" equals 3.atoms present obviously, there must be at least A similar type ofvcompound, which contains one basic nitrogen atom, provided that onlyparan ether linkage. is described in U. 8. Patent No. tial amidiiicationhas been employed. 2,259,704, dated October 21, 1941, to Monson and Asto the hydroxylated high molal amides, cue Anderson. In said patentthere is a description is concerned with the type of material which oiacylated aminoethers containing: may be, obtained as the oxyal-kylationderivative (a) A radical derived from a basic hydroxyof thecorresponding amide or substituted amide aminoether, and said radicalbeing of the kind For instance, any high molal acid r i s quivcontainingat least one amino nitrogen free from alent may be reacted with ammoniaor the like attached aryl and amido-linked acyl radicals; to produce anamide by conventional proced said hydroxyamino ether radical beingfurther However, amides, instead of being obtained from characterized bythe presence of at least one ammonia, may be obtained from primaryamines, radical derived from a basic hydroxyamine and such as amines inwhich a hydrogen atom linked being attached by at least one etherlinkage to to a nitrogen atom has been replaced by an at least oneradical selected from the class conrad al, an aralkyl radical, In alic iM lsisting of glycerol radicals, polyglycerol radicals, an alkylol racal or the type of radical in which polyglycol radicals, basichydroxyamine radicals, the carbon chain has been interrupted at leastamido hydroxyamine radicals, and aryl alkanolonce by an oxygen atom.Examples of such amine radicals, said 'basic hydroxyaminoether aminesare amylamine, cyclohexylamine, lradical being characterized bycontaining not amine, monoethanolamine, tris(hydroxymethyl)- over 60carbon atoms; and aminomethane, etc Polyamino types may also (b) An acylradical derived from a detergente employed, such as ethylenediamine,bis(byforming monocarboxy acid having at least 8cardroxyethyl)ethylenediamine, etc. If one starts bon atoms and not morethan 32 carbon atom th ammonia, or an amine free from a hysald acylatedaminoether being additionally char- 0 droxylated radical, it is obviousthat the amides acterized by the fact that said aforementioned soobtained, for instance, oleoamide, ricinoleoacyl radical is asubstituent for a hydrogen atom amide. amyloleoamide,amylricinoleoamide. or of an alcoholic hydroxy radical. the like, can betreated with one or more moles Although primarily, raw materials, suchas triof an oxyethylating agent such as ethylene oxide, ethanolamine,ethyldiethanolamine, and the like, 35 propyleneoxide, butyieneoxide,glycid, or the like, are most frequently employed in the manufacture togive a high molal substitu d amide having at of the acylatedaminoalcohol it is understod that least one monocarboxydetergent-forming acid such materials may be reacted with anoxyethylacyl radical and at least one hydroxylated hydroating agent,such as ethylene oxide, propylene carbon group, or the equivalent,wherein the oxide, or the like, to produce comparable macarbon atomchain isinterrupted at least once by terials which also are well knowncompounds. oxygen. The amine need not be basic, and thus (See also U. S.Patents Nos 2,228 986 7, 8, and 9, aniline, phenylethanolamine, or thelike may also all dated January 4, 1941, to De G oote, Keiser beemployed as a primary reactant. Obvious] and Blair) If desired, theacylated aminoalcoowever, amides can be obtained as conveniently hols ofthe kind previously described ma be subfrom a fatty acid, for example,and monoethanoliected to a subsequent oxyalkylation step i e amine, aswould be possible by first reacting the treatment with ethylene oxide orthe like For fatty acid or its equivalent, such as the ester, example,the ester derived from ricinoleic acid with ammonia, and thensubjecting-the unsuband triethanolamine could be subjected totreatstituted amide to oxyethylation. The production ment with ethyleneoxide, propylene oxide, or the of such amides, and as a matter of fact,polye As has been previously pointed out, such amides derived fromsuitable polyamines, is well acylated aminoalcohols containing at leastone own and requires no further elaboration. basic amino nitrogen atom,need not be obtained presence of a basic nitrogen atom, i. a nitrogenfrom monoamines or monoaminoalcohols, but atom not directly linked toeither an aryl group, may, in fact, be obtained from polyaminoalcoor anacyl radical, isnot objectionable, and may h h s, hydroxyethylethylenediamine may be desirable. For instance, one might react hybetreated with t e o es of ethy ene oxide, so droxyethyl ethylene diaminewith ricinoleic acid asto obtain tetra hydroxyethyl) ethylenediamine soas t introduce th acyl ra a digt Such product can be readily acylatedwith a guished from ,the acyloxy radical It is to high molal detergent-fg acid. Similarl noted that some of the high molal substituteddiethylenetriamine can betreated with four moles amides are polyfun floal m that two or more of ethylene oxide so as to yield atetrasubstituted hydroxy hydrocarbon radicals, or their equiv- Pmduct-The Obtained can be alents, are introduced Flirt ermore, there is-noated with two moles of a suitably selected deter- Objection t using hoxyeghyh agent in gent-forming acid, for example, a higher fattystanfial. mumple' pmpomom e there is no acid, to giveasuitable acylatedaminoalcohol havobjection t0 introducing an ether name which mg at leastbasic mtmge-n amms- Further recurs a number of times Although reactantsmore in the bmadest aspect" one is not mmted of the kind describedimmediately p eceding are to acylated derivatives in which the acyloxyradie Own a f w examples will be given. cal of the detergent-formingacid enters into the i aminoalcohol but one may employ compolmds BASICMy Am in which the acyl group. as distinguished from m menu the acyloxygroup, is introduced into the amino Example 1 reactant. For example,ethylenediamine, or diethylenetriamine, may be treated with a deter-Ricinoleic acid is reacted with triethanolamine in the conventionalmanner to give a compound of the following formula:

OHRCQOCIHI OHCIH N OHCIHQ BASIC Acvmmo Amosnconors Example 2 V The sameprocedure is followed as in the pre ceding example, except that thetriethanolamine is treated with three moles of ethylene oxide prior toacylation with ricinoleic acid.

BASIC AcYLArnp AMINOALCOHOLS Example 3 Ethyldiethanolamine issubstituted for triethanolamine in Examples 1 and 2, preceding. I

BASIC ACYLATED AmmoALconoLs Example 4 'Iriisopropanolamine orpropyldiisopropanolamine is employed, following. the same procedure asdescribed in Examples 1 to 3, preceding.

BASIC Acumen AMINOALCOHOLS Example I-lydroxyethyl ethylenediamine isreacted with three moles of ethylene oxide and then with one mole ofricinoleic acid, so as to give a compound of the following composition:

HYmroxYLArEn Sussnmnn I-Iron Monu- Amnns Example 2 One pound mole ofricinoleic acid isreacted with one pound mole of diethanolamine to givethe corresponding amide. v I-Iruxoxrm-run SUBSTITUTED HIGH Example 3 Onepound mole of ricinoleic acid is reacted with one pound mole of2-amino-2-methyl-1,3- propanediol to give the corresponding amide.

Mour- Amns Hmmoxrmrnn Suasrrrurn Eran Mom AIHDES Example 4 One poundmole of ricinoleic acid is reacted with one pound mole of2-amino-2-ethyl-1,3- propanediol to give the corresponding amide.Himaomsrsn Srms'rrru'rn Hrcn Mom AIIDES Example 5 One pound mole ofricinoieic acid is reacted witlr one pound mole of tris(hydroxymethyl)-aminomethane to give the corresponding amide.

Hrnnoxxu-rsn Example 6 One pound mole of diamine to give thecorresponding amide. HYDROXYLATED Suns'rrru'rnn HIGH MOLAL AminesExample 7' One pound mole of diethylenetrlamine isreacted with one poundmole of ricinoleic-acid to give the corresponding amide, which is thenreacted with one pound 'mole of ethylene oxide to give the correspondinhydroxyethylamide.

Returning now to consideration of acylated products by reactioninvolving reactants exemplified by Intermediate Examples 1 to 10,inclusive,

one need only consider a few specific examples, such as the following,which illustrate procedure so that more elaborate description isunnecessary:

ACYLATED Paonuc'r, EXAMPLE 1 Three pound moles of a material of the kinddescribed .under Intermediate product, Example 1, preceding, was heatedfor approximately 2 hours at 200 C. with one pound mole oftriricinolein.

ACYLA'IED Psonuor, EXAMPLE 2 The same procedure was followed as in Acyproduct, Example 1, preceding, but instead of using Intermediateproduct, Example 1,preceding,

there was substituted various other intermediate products, as describedunder the heading Intermediate product,.Exa:mple 2 to Intermediateproduct, Example 10, inclusive.

ACYLATED Pnouuo'r, EXAMPLE 3 In view of the composition of some of theproducts described under ,Intermediate products, Examples 2l0,"preceding, it is obvious that more than one acyl radical could beintroduced. For instance, three pound moles of an intermediate productof thekind exemplified by Intermediate product, Example 1, was reactedwith two pound moles of triricinoiein, so as to yield a polyacylatedproduct. 7

Aom'ran Paonucr, EXAMPLE 4 Two poundmoles of ethanol ricinoleoamideobtained by reaction between ricinoleic acid and ethanolamine, wereheated with one-pound moleof diethyl carbonate. (See Hydroxylatedsulbstituted high molal amide, Example 1.) The reaction was conducted inthe presence of /2% sodium carbonate as a catalyst. The material wasrefluxed at approximately C. for 8 hours,

and then the distillate removed in the customary manner.

Aoxnarnn Pnonuc'r, Ehmmrnn 5 Diethyl ricinoleoamide derived by reactionbe-' tween ricinoleic acid and-diethanolamine .was

substituted for ethanol ricinoleoamide in the pre ceding example. (SeeHydroxylated substituted high molal amide, Example 2.) Approximatelyone-half percent of sodium bicarbonate was added as a catalyst duringthe reaction.

Acxu rnn Pxonucr, EXAMPLE 6 The amide derived by reactionbetween'rioinoleic acid and tris(hydroxymethyl) aminomethane wassubstituted for diethanol ricinoleoamide in the preceding example. (SeeHydroxylated substituted high molal amide, Example 5.) Approximatelyone-half precent of sodium bicarbonate was added as a catalyst duringthe reaction.

Sussrrrurnu HIGH MOLAL AMIDES ricinoleic acid is reacted with one poundmole of hydroxyethyl ethyleneerence is made to the following examples:

Acxmrrn PnonUcnExAuPLr: 7

Two pound moles of a type of material exemplifled by Basic acylatedamino alcohols, Example 1, is reacted .with one and removed in thecustomary Acxursn PRODUCT, EXAMPLE 8 Two pound moles of materialsexemplified Basic acylated amino alcohols, Example 2, are reacted withone pound mole of diethyl carbonate in the same manner as precedingExample 7.

Acxnsran Pnonuc'r, EXAMPLE 9 'Iiwo pound moles of material of thekindexmanner as in Example 7, immediately precedmg As has been previouslypointed out, any of the high molal monocarboxy detergent-forming acidcompounds may be employed' teaseed oil, linseed oil, corn oil,cottonseed oil, and the like, would be particularly desirable,

suitable compoun naphthyiamine, aniline, cyclohexylamme ethylcycloh'exylamine, fdicyclohexylamine, benzylamine, ethyl benzylamine,etc.

- ucts, may be considered as intermediates for subsequent and furtherreaction, For instance, they or polybasic acid may be combined withdibasic or phthalic acid,

maieic acid, citraconic acid,'and the like, to produce resinous andsub-resinous materials. -",I'hey various uses previously enu-' byradicals which, in turn.

may be combined with such as ethyl chloroacetate, so as such variousderivatives are eilective demulsiiiers V for crude oil emulsions oi the.water-in-oil type. Furthermore, the introduction of a low molal acylradical, for instance, the introduction 01 low molal acid radicals arebest introduced by use of the esters, such as ethyl acetate. as areactant.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

1. The cylated derivative aminoalcohol ester of carbonic acid; in saidester all carbonicacid hydrogen atoms being replaced are the residues ofaminoalcohols exclusive or a hydroxyl group, and

acid having at least 8 and not more than 32 carbon atoms.

0 -o-o-obeing joined to the radical in which R is a member 01' alkyleneand alkyleneoxyalkylene radicals in hydrogen atom 01 said aforementionedhydroxylated carbonic acid ester being that or a detergent-formingmonocarboxy least 8 and not, more than 32 carbon atoms.

lathe acyl radical of a higher fatty acid having 18 carbon atoms and atleast one ethylene linkage.

5. The acylated derivative of a bydroxylated oalcohol ester of carbonicacid, as described in claim 2, wherein R2CO is higher fatty acid having18 of a hydroxylated having not over 6 ultrathe class consisting of inclaim 2, wherein RzCO is the acyl radical of a 5 higher fatty acidhaving 18 carbon atoms and at least. one ethylene linkage, and alloccurrences of R represent an ethylene radical, and the divalent radicalR0 of the radical I no B N R is joined to a hydrogen atom.

'7. In the manufacture of acylated esters of the kind described in claim1, the steps of reacting a leyv molal dialkyl carbonate with a tertiaryalkanolamine, and subsequently acylating the preceding resultant with ahigh molal nonocarboxy detergent-forming acid compound in which the acylradical contains at lea carbon atoms.

st 8 and not more than 32 MELVIN DE GROOTE. BERNHARD autism.

